高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (8): 1399.

• 研究论文 • 上一篇    下一篇

(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇及其酯和卤代物的合成与表征

吴军政1,2, 王克亮1, 康万利1, 朱东升3   

  1. 1. 大庆石油学院石油工程学院, 大庆163318;
    2. 大庆油田有限责任公司技术发展部, 大庆163453;
    3. 东北师范大学化学学院, 长春130024
  • 收稿日期:2004-10-29 出版日期:2005-08-10 发布日期:2005-08-10
  • 通讯作者: 康万利(1963年出生),男,研究员,博士生导师,主要从事油田化学及高分子合成研究.E-mail:kangw anl i@126.com E-mail:kangw anl i@126.com
  • 基金资助:

    国家自然科学基金(批准号:10172028);黑龙江省杰出青年科学基金(批准号:J03-11)资助.

Synthesis, Characterization and Crystal Structures of (Z)-1-[2-(Triphenylstannyl)vinyl]-1-indanol, Its Ester and Phenylhalostannyl Derivatives

WU Jun-Zheng1,2, WANG Ke-Liang1, KANG Wan-Li1, ZHU Dong-Sheng3   

  1. 1. Petroleum Egineering School, Daqiing Petroleum Institute, Daqing 163318, China;
    2. Department of Technical Development of Daqing Oilfied Corp. Ltd., Daqing 163453, China;=
    3. Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2004-10-29 Online:2005-08-10 Published:2005-08-10

摘要: 在氮气保护下,1-乙炔茚满醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇(1);将加成物(1)与苯酐反应,得到新型邻苯二甲酸单酯有机锡衍生物(2);衍生物(2)分别与二丁基氧化锡和三苯基氧化锡进行脱水反应,分别获得两个新型邻苯二甲酸酯的有机锡衍生物(3)和(4).将加成物(1)与卤素反应后,与锡原子直接相连的苯基被取代,得到一卤代和二卤代物(5~10).通过元素分析、1HNMR和IR等手段对化合物1~10进行了结构表征,确定了该类邻苯二甲酸单酯和邻苯二甲酸酯的有机锡衍生物的结构.并测定了加成物(1)和一溴代物(6)的晶体结构,在加成物(1)中,由于分子内存在较弱的O→Sn[0.2778(8)nm]配位作用,锡原子呈扭曲三角双锥构型.在一溴代物(6)分子中,存在分子内O→Sn[0.2364(2)nm]配位键,锡原子呈扭曲的三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物>加成物.

关键词: 有机锡(IV), 酯, 合成, 晶体结构

Abstract: (Z)-1-[2-(Triphenylstannyl)vinyl]-1-indanol 1 was synthesized by the additive reaction of 1-ethynylindanol with triphenyltin hydride. Compound 1 was esterified by phthalic anhydride to yield monoester derivative 2. Compounds 3 and 4 were prepared by the reaction of the monoester 2 with dibutyltin oxide and triphenyltin hydroxide, respectively. The phenyl groups in compound 1 were substituted by ICl, Br2 or I2 to yield mono-and dihalide derivatives(5-10). Compounds 1-10 were characterized by elemental analysis, 1HNMR and FT-IR spectroscopy. The crystal and molecular structures of compounds 1 and 6 were determined by single crystal X-ray diffraction analysis. The Sn atom in compound 1 exhibits a distorted trigonal bipyramidal structure due to a weak intramolecular interaction between Sn and the hydroxyl O atoms [0.277 8(8) nm], while the Sn atom in compound 6 adopts a trigonal bipyramidal geometry with a significant Sn1←O interaction [0.236 4(2) nm]. The Lewis acidities of the Sn atoms are in the following order: PhSnX2L>Ph2SnXL>Ph3SnL.

Key words: Organotin(Ⅳ), Ester, Syntheses, Crystal structure

中图分类号: 

TrendMD: